S of anthranilic acid normally solid crystalline polypropylene stabilized by aromatic ester

ABSTRACT

(HO,R&#34;&#34;-PHENYL)-X-   WHEREIN R&#34;&#34; IS H OR AN ALKYL GROUP OF 1 TO 20 CARBON ATOMS, X IS $S$N, OR   -(CH2)N-N(-R)-(CH2)N&#39;&#39;-   WHERE N HAS A VALUE FROM 1 TO 5, SAID ESTER OF ANTHRANILIC ACID BEING PRESENT IN AN AMOUNT SUFFICIENT TO ENHANCE THE STABILITY OF SAID COMPOSITION AGAINST UV AND HEAT DEGRADATION.   IN WHICH R AND H ARE AN ALKYL GROUP OF 1 TO 4 CARBON ATOMS, R&#39;&#39; AND R&#34; AND H, NO2, ALKYL GROUPS OF 1 TO 20 CARBON ATOMS, HALOGENS, AND ALKOXYL GROUPS OF 1 TO 20 CARBON ATOMS, R&#34;&#39;&#39; IS AN ALKYL GROUP OF 5 TO 20 CARBON ATOMS EITHER STRAIGHT OR BRANCHED CHAIN IN STRUCTURE, AND Y HAS THE STRUCTURE:   1-((Y,R&#39;&#39;,R&#39;&#39;&#34;-PHENYL)-OOC-),2-(R-NH-),R&#34;-BENZENE   NORMALLY SOLID CRYSTALLINE POLYPROPYLENE IS STABILIZED BY ESTERS OF ANTHRANILIC ACID OF THE FORMULA:

United States Patent Office 3,758,437 Patented Sept. 11, 1973 US. Cl.260-4585 A 3 Claims ABSTRACT OF THE DISCLOSURE Normally solidcrystalline polypropylene is stabilized by esters of anthranilic acid ofthe formula:

in which R is H or an alkyl group of 1 to 4 carbon atoms, R and R" andH, N alkyl groups of 1 to 20 carbon atoms, halogens, and alkoxyl groupsof 1 to 20 carbon atoms, R' is an alkyl group of 5 to 20 carbon atomseither straight or branched chain in structure, and Y has the structure:

X O RI!!! wherein R is H or an alkyl group of 1 to 20 carbon atoms, X isQS%1, or

R f I f V. N where n has a value from 1 to 5, said ester of anthranilicacid being present in an amount snfficient to enhance the stability ofsaid composition against UV and heat degradation.

CROSS-REFERENCE TO RELATED APPLICATION This application is acontinuation-in-part of US. application Ser. No. 102,968, filed Dec. 30,1970 now abandoned.

FIELD OF INVENTION This invention relates to normally solid crystallinepolypropylene compositions of enhanced stability containing aromaticesters of anthranilic acid as stabilizers and certain aromatic esters ofanthranilic acid as novel compounds.

DESCRIPTION OF INVENTION The novel compositions of this inventioncomprise normally solid, substantially crystalline polypropylene and aminor proportion of ester of anthranilic acid having the generalstructure:

O R!!! RI! Y N HR in which R is H or an alkyl group of 1 to 4 carbonatoms, R and R are H, N0 alkyl groups of 1 to 20 carbon atoms, halogens,and alkoxyl groups of 1 to 20 carbon atoms, R' is an alkyl group of 5 to20 carbon atoms either straight or branched chain in structure, and Y isH or has the structure:

X H 0 RIIII wherein R"" is H or an alkyl group of 1 to 20 carbon atoms,X is {Si or {CHfiJhfCH -h where n an n may be the same or different andhave a value from 1 to 5, said ester of anthranilic acid being presentin an amount sufficient to enhance the stability of said compositionagainst UV and heat degradation.

The novel stabilizers of this invention are aromatic esters ofanthranilic acid of the formula;

0 (LO R" Y NHR in which R is H or an alkyl group of 1 to 4 carbon atoms,R and R are H, N0 alkyl groups of 1 to 20 carbon 'atoms, halogens, andalkoxyl groups of 1 to 20 carbon atoms, R' is an alkyl group of 5 to 20carbon atoms either straight or branched chain in structure, and Y hasthe structure:

X HO RI!!! wherein R" is H or an alkyl group of 1 to 20 carbon atoms, Xis {Si or R f l \V. N

where n and 11' may be the same or different and have a value from 1 to5.

The aromatic esters of anthranilic acid of this invention are made byheating a mixture of a phenol with isotoic anhydride until the evolutionof carbon dioxide ceases. The reaction is as follows:

The following examples illustrate the aromatic esters of anthranilicacid and normally solid, substantially crystalline polypropylenecompositions containing them. Unless otherwise indicated, theproportions are on a weight basis.

Example 1.-Preparation of 2,2'-thiobis(4-octylphenol) monoester ofanthranilic acid In a 250-1111. Erlenmeyer flask on a heater withmagnetic stirrer, 4.05 g. (25 mmoles) of isatoic anhydride,

11.05 g. (24 mmoles) of 2,2'-thiobis(4-octylphenol) and 0.05 g. ofpowdered sodium hydroxide were stirred in 150 ml. 1,4-dioxane and slowlyheated to reflux for one hour. The reaction mixture was then cooled,poured into 600 ml. water, and ether extracted. After evaporating todryness and obtaining a weight of 13.6 g. (97% of theory), the materialwas crystallized from methanol to yield 1.3 g. of2,2'-thiobis(4-octylphenol) monoester of anthranilic acid as light tanglobules, melting point 155.5156.5 C. Calculated for C35H47NSO3(percent): C, 74.81; H, 8.43; N, 2.50; S, 5.70. Found (percent): C,74.55; H, 8.24; N, 2.51; S, 5.88.

The infrared spectrum contained two sharp NH bands at 3500 cm.- and 3380cmr a small broad OH band at 3425 crnf and an aromatic ester carbonylband at 1705 cm.

The UV spectrum contained two absorptions above 2400 A.: at 2900 A.(e=5400) and 3400 A. (6:6000).

Other aromatic esters of anthranilic acid were prepared by the generalmethod described in Example 1. The compounds of the examples and theirevaluation in normally solid, substantially crystalline polypropyleneare set out in the following table.

4 blenders. Minor amounts of other polymers, pigments, photostabilizers,oxidation stabilizers, heat stabilizers, dye acceptors, dyes, fillers,and the like may also be incorporated into these mixtures.

The normally solid, substantially crystalline polypropylene which isstabilized by the aromatic esters of anthranilic acid in accordance withthis invention is a wellknown commercial commodity. It is normally atleast about 85% crystalline. It is essentially insoluble in refluxingheptanes.

As indicated in the above table, each of the aromatic esters ofanthranilic acid was mixed with polypropylene powder at a concentrtionof 0.5 percent. The dry mixture was pressed into 20-mil thick sheets.The sheets were tested in an oven at 138 C. to determine their life asexpressed in hours. The polypropylene sheets were also exposed to afluorescent sunlamp-black light Weather- Ometer and flexed periodicallyto obtain a time to fiexural failure.

While the character of this invention has been de scribed in detail withnumerous examples, this has been done by way of illustration only andwithout limitation TABLE 0.5% in polypropylene time to sample failure138 C. R R R 1 R 1 Y 2 oven, hr. FS/BL, hr.

Example number:

1 H H 8 8 S"' 615 1,235 H 8 H 20 1, 250 H 8 8 S* 144 317 C1 8 8 -S--*750 167 NO: 8 8 -S* 960 408 H 12 12 -SS-" 884 500 H 8 8 CHz-NClPIa(L:I2-" 126 473 1 Numbers refer to number of carbon atoms in correspondingR' and R alkyl groups of structural formulae.

2 =Phenolic group having the structure HO g RI!!! n the above formulae.

Example number R R R" R' R Y 10 H H; CwHzi 8 8 SS' 11 C3H7 CH3 C411 1212 S* 12 H CrzHzs CH3 8 12 S-- As already mentioned, the aromatic estersof anthranilic acid of this invention have a remarkable ability toenhance the resistance of normally solid substantially crystallinepolypropylene to .UV and thermal degradation. In the preparation ofsuitable polypropylene compositions the aromatic esters of anthranilicacid are mixed homogeneously with such polypropylene at concentrationsof at least about 0.05 percent by weight and usually from about 0.05 to0.50 percent by weight based on the polypropylene. Homogeneous mixing isachieved by blending the polymer and the ester in powder form inconventional powder blenders or by mixing them in conventional melt ofthe invention. It will be apparent to those skilled in the art thatmodifications and variations of the illustrative examples may be made inthe practice of the invention within the scope of the following claims.

I claim:

1. Composition comprising normally solid, substantially crystallinepolypropylene and a minor proportion of ester of anthranilic acid havingthe general structure:

in which R is H or an alkyl group of 1 to 4 carbon atoms, R and R" areH, N0 alkyl groups of 1 to 20 carbon atoms, halogens, or alkoxyl groupsof l to 20 carbon atoms, R is an alkyl group of 5 to 20 carbon atomseither straight or branched chain in structure, and Y has the structure:

HO RI!!! 5 6 wherein R"" is H or an alkyl group of 1 to 20 carbonReferen e Cit d awms X13673 UNITED STATES PATENTS 3,022,268 2/1962Armitage et al. 26045.95 T T 7T' 5 2,853,423 9/1958 La. Vie 4246() E3,214,399 10/1965 Saccomandi 26045.95 where n and It may be the same 01dlfierent and have a 2 02 10 957 Bill 2 0 45 9 value from 1 to 5, saidester of anthranilic acid being 3,653 374 4/1972 Bevilacqua 26O 45 85present in an amount sufi'icient to enhance the stability of u I saidcomposition against UV and heat degradation. FOREIGN PATENTS 2. Thecomposition of claim 1 wherein the aromatic 10 903,015 8/1962 GreatBritain. ester of anthranilic acid has Y of the structure:

DONALD E. CZAJA, Primary Examiner HO R V. P. HOKE, Assistant Examiner 3.The composition in accordance with claim 2 in which 26 71 R R" and R"are alkyl groups of 8 carbon atoms each.

